A5000731138- Radical Photochemical Reactions
- Catalytic C–H Functionalization Methods
- Conducting polymers and applications
- Organic Electronics and Photovoltaics
- Synthesis and Properties of Aromatic Compounds
- Synthetic Organic Chemistry Methods
- Sulfur-Based Synthesis Techniques
- Catalytic Alkyne Reactions
- Electrochemical Analysis and Applications
- Catalytic Cross-Coupling Reactions
- Synthesis and Catalytic Reactions
- Luminescence and Fluorescent Materials
- Cyclopropane Reaction Mechanisms
- Supramolecular Chemistry and Complexes
- Fullerene Chemistry and Applications
- Chemistry and Chemical Engineering
- Organoboron and organosilicon chemistry
- Crystallization and Solubility Studies
- Free Radicals and Antioxidants
- Organic Light-Emitting Diodes Research
- Carbon dioxide utilization in catalysis
- Oxidative Organic Chemistry Reactions
- Advanced Sensor and Energy Harvesting Materials
- Chemical Synthesis and Analysis
- X-ray Diffraction in Crystallography
University of California, San Diego
2021-2025
Massachusetts Institute of Technology
2019-2021
University of North Carolina at Chapel Hill
2014-2016
Calvin University
2012
Over the past several decades, organometallic cross-coupling chemistry has developed into one of most reliable approaches to assemble complex aromatic compounds from preoxidized starting materials. More recently, transition metal-catalyzed carbon-hydrogen activation circumvented need for materials, but this approach is limited by a lack practical amination protocols. Here, we present blueprint functionalization via photoredox catalysis and describe utility strategy arene amination. An...
Herein, we report half-peak potentials for over 180 organic substrates obtained via cyclic voltammetry. These values are of great use in assessing the thermodynamics an electron-transfer process. In addition, disclose a simple computational method to determine redox substrates.
We describe our efforts to understand the key mechanistic aspects of previously reported alkene hydrofunctionalization reactions using 9-mesityl-10-methylacridinium (Mes-Acr+) as a photoredox catalyst. Importantly, we are able detect cation radical intermediates, and confirm that phenylthiyl is capable oxidizing persistent acridinyl in fast process unites catalytic activity hydrogen atom transfer (HAT) manifolds. Additionally, present evidence diphenyl disulfide ((PhS)2) operates on common...
A new Au(III)-catalyzed tandem amination-hydration reaction has been discovered, leading to the formation of α-(N-2-pyridonyl)ketones and heterocyclic analogues in good excellent yields (14 examples, 48-90%). This demonstrates unusual use a sp(2) nitrogen nucleophile gold-catalyzed 6-endo-dig cyclization. The process allows rapid access α-(N-2-pyridonyl)ketones, making them convenient building block for synthesis more complex N-alkyl pyridone targets.
Efficient syntheses that incorporate thiophene units into different extended conjugation systems are of interest as a result the prevalence sulfur-rich aromatics in organic electronics. Self-organization by using liquid crystal properties is also desirable for optimal processing electronics and optical devices. In this article, we describe two-step process to access regioisomers polyaromatics with shapes. This method involves an efficient single or double benzannulation from alkyne precursor...
Aromatic diisocyanates, invaluable commodity chemicals for polymer manufacturing, are produced annually on megaton scales from petroleum‐derived diamines via phosgenation. Existing routes toward renewable alternatives sparse and limited by access to functionalized aromatic starting materials, such as terephthalates. Herein, we report the development of a robust route terephthalates diisocyanates D‐galactose Eastwood olefination Diels‐Alder cycloaddition, followed mild electrochemical...
Aromatic diisocyanates, invaluable commodity chemicals for polymer manufacturing, are produced annually on megaton scales from petroleum‐derived diamines via phosgenation. Existing routes toward renewable alternatives sparse and limited by access to functionalized aromatic starting materials, such as terephthalates. Herein, we report the development of a robust route terephthalates diisocyanates D‐galactose Eastwood olefination Diels‐Alder cycloaddition, followed mild electrochemical...
Abstract Crosslinking is a ubiquitous strategy in polymer engineering to increase the thermomechanical robustness of solid polymers but has been relatively unexplored context π‐conjugated (semiconducting) polymers. Notwithstanding, mechanical stability key many envisioned applications organic electronic devices. For example, wide‐scale distribution photovoltaic devices incorporating conjugated may depend on integration with substrates subject insult—for road surfaces, flooring tiles, and...
The conductive polymers poly(3,4-ethylenedioxythiophene) (PEDOT) and polypyrrole are widely used in organic optoelectronic, bioelectronic, electrochromic applications. However, a general process for forming highly films with high spatial resolution on various substrates is lacking. This work describes technique PEDOT using vapor-phase polymerization (VPP). process, reminiscent of classical black-and-white photography, employs photosensitive VPP initiating film. UV light selectively...
Polymeric materials bearing Frustrated Lewis Pair (FLP) functionality are promising candidates for use as heterogeneous catalysts and adaptive materials, but synthetic access to FLP-functional polymers remains limited due the incompatibility of FLPs with standard polymerization chemistries. Herein, we describe a approach that "cages" highly reactive vicinal phosphine-borane covalent alkene adducts, which stable Ni-mediated vinyl addition polymerization. We discovered caged FLP adducts can be...
Poly(p-phenylene sulfide) (PPS) is a highly robust thermoplastic with outstanding thermal and chemical stability. However, development of functional PPS-based materials hampered by harsh synthetic conditions poor solubility. As an alternative to nucleophilic aromatic substitution (SNAr), we report herein on the use benzoquinone conjugate addition chemistry prepare PPS derivatives bearing redox-active hydroquinones in polymer backbone. Specifically, utilize thiosilanes as thiol surrogates...
Abstract The design and synthesis of new macrocycles with well-defined cavities represent a promising avenue for the development supramolecular hosts. Moreover, ability to diversify macrocycle through chemical manipulations enables fine-tuning tailoring properties. In this report, functionalization thiapillar[6]arene, pillar[6]arene analogue in which bridging methylene groups are replaced by sulfurs, described. First, we demonstrate scalable parent thiapillar[6]arene. Next, diversification...
N-Heterocyclic carbene pentafluorophosphorus (NHC-PF
Engineering thermoplastics feature high chemical, mechanical, and thermal robustness but often lack advanced functionalities as a result of the harsh conditions required for their synthesis processing. Herein, we introduce series polyarylene chalcogenides (PACs), classification which encompasses polyphenylene sulfides, oxides, derivatives, obtained via room-temperature polymerization difluorophthalonitrile disilyl(thio)ether monomers in presence fluoride or amine initiators. The PACs contain...
Abstract Acridinium salts catalyze the TEMPO‐mediated amination of arenes under light irradiation.
Abstract Review: 579 refs.
Abstract The silyl ether (IIb) decomposes and only 2‐pyridone is formed.
Key words helical structures - polycyclic aromatics thiophenes Newman–Kwart rearrangement
Key words azaaromatics - organoboron compounds electrophilic aromatic substitution